Processing of synthetic hydrocarbons



April 15, 1952 l. MALM PROCESSING OF' SYNTHETIC HYDROCARBONS 2 SHEETS-SHEET l Filed March 9, 1948 9530 NONI' om l INVENTOR IGNACE ATTO R N EY Patented Apr. 15, 1952 PROCESSING OF SYNTHETIC HYDROCARBONS Ignace L. Malm, Tallant, Okla., assignor to Cities YService Oil Company, Bartlesville, Okla., a corporation of Delaware Application March 9, 1948, Serial No. 13,924

1 invention relates to improvements in the processing of the products synthesized by processes of the type of the Fischer-Tropsch, Synthol or Synthina More particularly my process relates tothe separation of the various chemical .compounds produced by such synthetic procobtained.. While the oily and aqueous products have been processed separately for the recovery of various chemical constituents, I iind that there is considerable advantage to processing the hydrocarbon fraction to a certain point along with the aqueous productcontaining vwater soluble chemicals. However, at an early stage in my process, I preferably separate out the hydrocarbon materials in two process streams andthereafter combine the recovery and refining' of the various oxidized hydrocarbon compounds in a proces-s which I find greatly reduces the `loss of alcohols and acids due to esteriiication.

An important feature of my invention therefore involves the substantially separate processing of the alcohols and acids except for particularvcombined operations as pointed out hereinafter.

lThe primary object of my inventionis to provide an improved process for the handling of synthetically produced chemicals, such as those obtained by the Fischer-,Tropsch process.

Another object of my inventionis to provide an improved process in .which loss of alcohols and acids due to esterication is substantially avoided. l

The details of myk process are set out hereinafter in connection with the accompanying drawings which form a part of this application.

In the drawings:

Figures 1 and 1a taken together comprise a diagrammatic view partly in elevation showing an vassembly of apparatus elements constructed and arranged in a flow sheet form suitable for carrying out my improved process.

In accordance with the features of my invention, the mixture of oily and aqueous products direct from the Synthol process is introduced into the apparatus through a line 2, or a correspending mixture taken from the Synthol oil supply andthe Synthol aqueous product, s up- 4 Claims. (Cl. 260-450) ply 4 may be conducted into the line 2, and thereby into a fractionatlng tower 5 of the appa-.- ratus. The products taken from thesupplies 3 and 4 are advantageously mixed in approximately the proportions in which they are formed in the process. The fractionation carried out in tower 5 is preferably conducted at a toptemperature of from 80 C. up to about 95 C. In most cases the higher temperature will be employed and the reflux ratio maintained so that. substantially all of thealcohols are taken overhead while substantially all of the acids are retained in the tower 5 and withdrawn as a bottoms product into a separator 6. 'This bottoms product comprises hydrocarbon and aqueous fractions each containing dissolved oxygenated chemicals which are separated in the separator 6. These fractions are respectively withdrawn` through lines 8 and 1 and processed along with some of the overhead products vin accordance with the proces dure described hereinafter in connection, with the portion of the apparatus shown in Figure 1a. :The vapor mixture taken overhead from the `tower 5 is condensed in a condenser, as indicated,

f head condensate is refluxed to the tower 5 to control the fractionation. Y

'Ihe hydrocarbon fraction separated out in the separator 9 is passed into extractor III wherein the water soluble constituents are `washed from the hydrocarbon fraction with water. 'I'he hydrocarbon fraction is removed `continuously from the extractor I0 intov a caustic treater II, and therein agitated With 20 per cent caustic solution for the hydrolysisof esters and removal of impurities and oxygenated hydrocarbons, including organic acids, not removed in the extractor I 0. The acids are converted to salts. The combined materials in the treater II are conducted into a separator I2 for the separation of the caustic washings from the hydrocarbon fraction.` The caustic washings are withdrawn through a line I3 and subjected to further processing with some of the bottoms products withdrawn from the separator 6 into the portion of the apparatus shown in Figure 1a. l

- The hydrocarbon fraction withdrawn from the separator I2 is conducted into an ethylene glycol extractor I4 in which the hydrocarbons are substantially freed oi organic oxygen containing compounds, such as alcohols,` aldehy'desl and ketones. The extraction effected inthe extractor head the extracted organic compounds and wai ter, while the ethylene glycol is removed from the bottom of the stripper and recirculated to .the top of the extractor I4, as indicated.

'I'he aqueous stream containing the organic compounds'removed overhead from the still I5 is condensed and mixed with the water washings from the extractor I and the separated aqueous layer from the .separator 9. This mixture is conducted into a fractionating tower Il which is used as an aldehyde still. The low boiling aldehydes present in the mixed products introducedinto the fractionating tower I'I and com- 'prising primarily acetaldehyde and propionaldehyde are fractionated out overhead under controlled conditions along with some of the water contained in the mixture. The bottoms productproduced in the still II is conducted into afractionating still I8, which is used primarily for the separation overhead of methyl acetone. The stills Il and I8 are each associated with suitable condensers, as shown, and provision is made for adequate reuxing.

' The bottoms product stream from the fractionating still or tower I8 and containing primarily alcohols and small proportions of ketone and aldehyde impurities is conducted into a hydroxyalkylator I9 for condensation of the ketone and aldehyde impurities into polymer products in the presence of caustic alkali or l other alkaline agent. The entire mixture producedrin the alkylator I9 is conducted into a ash still for the removal of alcohols from the polymer and waste materials which are withdrawn from the bottom of the still 20. l The alcohols and water taken overhead from the still 20, are conducted into a fractionating tower 2l for the separation overhead of the ethanol content of the mixed alcohols. The bottoms from the ethanol still 2I are conducted into a rerun still 22 which is operated and controlled so as to take overhead primarily propanoL, butanol and small proportions of higher alcohols. 'Water and dissolved higher alcohols are removed from the bottom ofthe still 22 for further processing after a sufficient accumulation.

The overhead vapors from the still 22 are conducted into a dehydrating still 23 in which a suitable azeotropic entrainer (such as benzene) is introduced and used to carry over the water `from the alcohol mixture. This still is associated with a separator 24 and a water stripper 25; the overhead product from the still 23 being water layer with small proportions of water soluble Vconstituents is conducted into the stripping still 25 which drives overhead alcohol constituents, azeotropic entrainer and water, which lare returned to the separator 24, while most of, thevwater is withdrawn from the bottom of the stripper 25.

The dehydrated alcohol streamv produced by the still 23 is withdrawn as a bottoms product and conducted into a propanol still 26 from which normal propanol is recovered overhead as a substantially dry and clean fraction. The bottoms product of higher boiling point is withdrawn from the fractionating still 25 into a fractionating still 2l for the removal overhead of n-butanol. This butanol product is substantially anhydrous and a relatively clean fraction. The higher boiling alcohols are withdrawn as a bottoms product from the still 2l and may be accumulated for fractionation so as to separate the various individual higher alcohols from each other.

The bottoms products removed from the fractionating tower 5 and recovered in the separator 6, together with some of the products taken overhead, are processed in accordance with the showing in Figure la of the drawings. The oil fraction separated out in separator 6 of Figure l and removed through the line 8 is conducted into a caustic alkali treater 28 in which the oily fraction is agitated thoroughly with a caustic alkali solution which converts the organic acids into salts and hydrolyzes the esters, which then yield alcohols and salts of the acids. The acid-free loil fraction is removed overhead from the treater 28, while the caustic solution containing the salts of organic acids is withdrawn into a salt solution stripping still 29 for removal of volatile impurities which are distilled overhead. The alkaline salt solution is withdrawn from the still 29 and passed into an acidiiier 30 into which sulfuric acid is introduced and used to convert the salts of organic acids into organic acids. The caustic extract separated out in the separator I2 in Figure 1 and containing salts of organic acids removed from the oil fraction processed in the caustic treater II is conducted through the line I3 and mixed with the salt solution introduced into the acidier The aqueous fraction withdrawn from thc separator 6 in Figure 1 and conducted therefrom through the line 'I is processed, as shown in Figure la, by conducting the mixture into a stripping still 3| for the removal of its small content of higher alcohols, aldehydes and ketones. These materials are vaporized overhead,

Ycondensed and collected in a separator 32 where the water insoluble higher alcohols, aldehydes and ketones separate from the water solution of organic acids which were carried overhead. The latter solution is removed from separator 32 and returned to the still SI while the upper layer is conducted into a caustic treater 33 where the mixture is intimately contacted with 10 per cent caustic solution for washing out any organic acids which may have been dissolved in the upper layer and separated in separator 32. The mixture from the treater 33 is conducted into a salt solution stripper 34 which is operated so as to remove overhead for condensation and collection, the high molecular weight alcohols, aldehydes and ketones. This mixture is preferably introduced into the still Il or I3 vin Figure 1 for processing with materials there- .regenerated -in the acidifier.

iiiit a'. puricauonstin as. The. purification Suu l311s operated in a manner similar to that of the v still- 23, using butyl acetate to effect the azeotropic distillation and purification of the lower` molecular weight acids@ TheV azeotropic mixture ofvaporstak'enoverhead arecondensed and sepv arated' in a separator 36 arranged so that the butyl acetate layer is conducted back into the still v35while. the water layer containing impurities and'dis'solved acids and butyl acetate, is conducted into an entrainer recovery still 31. The

TWater and impurities removed in the purifying operation is withdrawn to waste from the bottom of the still 31, while the vapors taken overhead Aare Acondensed with the vapors from the still 35 and the condensate sent to the separator 36 and .recycled to the azeotropic distillation system.

-Theacids are recovered as a bottoms product in the still35 and conducted into an acid treater 38, where they are intimately contacted with con- 'centrated sulfuric acid to remove carbonyl and other impurities.

`is conducted into a flash still 39 from which the The mixture from this treater purified organic acids are taken overhead into a lfractionating column 40. The residue obtained 4in the ash. still 39 is withdrawn as an acid sludge and may be sent to an acid recovery system.

. l The acidified mixture of organic acids and inlbottom of the iiash still 4| whilethe condensed higher molecular weight acids are conducted into `a purifying tower 42. This tower is operated in a-manner similar to that of the tower 35 and butyl acetate is used to effect the azeotropic distillation and purification ofthe acids. The overf Ihead vapors from the still 42 are condensed and sent to a separator 43 from which the butyl acetate layer and soluble acids taken overhead Vare returned to the tower 42, `while the water layer containingL primarily entrained butyl acetate and water soluble organic acids and impurities is conducted through a line 44 into the entrainer rccovery still 31 along with the water layer from the separator 36.

The acid mixture recovered in the bottom of the still 42 is conducted into an acid treater 45 for the continuous treatment of the stream of the acids with sulfuric acid for removal of carbonyl and other impurities.l The organic acids are intimately mixed with concentrated sulfuric acid in the treater 45 and conducted into a flash i still 46, while the overhead vapors-are condensed,

under vacuum conditions and thereby separated l'from'the sulfuric acid residue.. The acid residue or sludgeis withdrawn from the bottom of the still 46, while the overhead vapors are condensed, collected and the condensate passed into a stripping still 41 for the removal of lower aliphatic lacids from the higher molecular weight organic acids. The lower molecular weight acids are taken overhead through a line 48 and introduced into the still 40 along withthe lower molecular weight acids removed from the flash still 39. The higher molecular weight acids separated out in the still 41 are introduced into a fractional distilling tower 49.

The purified and acid-refined lower molecular weight organic acids introduced into the fractionating still 40 are processed under controlled fractionating condition to recover overhead the acetic acid content of the mixture. Propionic and butyric acids are respectively recovered in a. similar manner from the acid mixture in succeeding fractionating stills 50 and 5I by thefracation of the bottoms product from the preceding fractionating still. y The bottoms product recovered in the Afractionating still I and comprising organic acids of higher molecular weight than butyric acid are withdrawn through a line 52 and conducted into the fractionating still 43 along with the mixture of higher molecular Weight acids from the stripping still 41. The mixture of organic acids introduced into the fractionating still 49 are fracvalerio acids content of the mixture. Acids of higher boiling point are removed from the acid Vmixture in successive vacuum-operated fractionating Vcolumns 53, 54 and 55. Hexanoic acids are recovered overhead from the column 53, heptanoic acids from the column 54 and octanoic acids from the column '55. The organic acids of still higher boiling point remaining in the column 55 are withdrawn as a bottoms product for further treatment and fractionation when the quantity warrants sucha procedure.

From the foregoing description of the process for handling the stream of processed products produced by the Synthol synthesis, it will be seen that provision is made for recovering in a substantially pure state a great number of different chemicals including alcohols, aldehydes, ketones and organic acids as well as the hydrocarbons produced by the process. The combined handling of the hydrocarbons and the oil and water soluble constituents has the particular advantage that the alcohols and acids are effectively separated in the joint distillation, the rst step in the process, andV are vthereafterl 4processed separately 'so-as to avoid esterication and consequent loss of acids and alcohols. The alcohol stream is processed in such a Way as to remove` the acid impurities. which are taken at a particular point into the organic acid processing part of the system. The higher alcohols fractionated fromthe `acids are removed in a particular way and procand acids referred to above. In the particular example referred to,the ethanol content amounted to about 6 per cent by weight, the propanol to 1 .3 per cent and the n-butanol to about l per cent by weight. Acetic acid accounted for about 1.5 per cent while the original stream contained about 1 per cent each of Vpropionic and n-butyric acids. for the most part below 1 per cent. However, all of the percentages, if based upon the production of organic compounds, would be approximately doubled in view of the large proportion of water in the original stream. Some of the percentages may appear to be relatively low, but when it is realized that a large commercial "plant produces the 1product stream on a continuous be produced. The production, for example. of

The percentages of other materials were sumarios rn-lmtyric acid which was approximately l per cent'of the original stream, counting the water,

would run into a relatively large production in a full-sized commercial plant.

While benzene or butyl acetate has been referred to for use in effecting the azeotropic distillation in certain cases, it is to be understood that other selected materials may be used. For example, ethyl acetate may be used for extraction of the acids.

My improved process may be employed for the vhandling of mixtures of oxygenated hydrocarbons produced by other processes.

i Some modifications may be madein the handling of the various streams of materials being puriiied and fractionated without materially changing the overall nature of the process and -the various combined operations as described.

Such changes are contemplated as coming within the spirit and scope of my invention as defined by the appended claims.

I claim:

l. The process of purifying a mixture of syntlietically produced organic materials including hydrocarbons, oxygenated organicr compounds and water, which comprises subjecting the mixture of oily and aqueous products to a joint fractional distillation to recover an overhead product comprising light hydrocarbons, water, a large percentage of the carbonyls and alcohols contained in the charge stock and asmall percentage of the acids contained therein, and a bottoms product comprising heavier hydrocarbons, Water, a large percentage of the acids contained in the charging stock and a small percentage of the carbonyls and alcohols contained therein, separating the bottoms product into oily and aqueous layers,

subjecting the aqueous layer to a second fractional distillation, whereby to separate therefrom an overhead product containing carbonyls and alcohols, and a bottoms product containing organio acids, purifying the bottoms product by azeotropic distillation with butyl acetate, recover.

ing partially purified organic acids as a bottoms lproduct from the azeotropic distillation, further purifying the acids by treatment with concentrated sulfuric acid, and fractionating the resultant purified organic acids to recover their individual organic acid constituents in substantially pure form.

2. The process of purifying a mixture of synthetically produced organic materials including hydrocarbons, oxygenated organic compounds, and, water, including subjecting the mixture of oily and aqueous products to a joint fractional distillation to recover an overhead product comprising light hydrocarbons, Water, alcohols, and

carbonyls, and a minor proportion of the acids contained in the charge stock, and a bottoms product comprising heavier hydrocarbons, water, and the major portion of the acids contained linthe charge stock, separating the overhead product into an aqueous and oily layer, treating the oily layer with caustic solution to convert the acids present into their sodium salts, recovering the acid salts, separating the bottoms product into an aqueous layer and an oily layer, treating the bottoms oily layer with a caustic soda solution to convert the acids present into their respective sodium salts, recovering the acid salts, combining the acid salts from the bottoms oil layer with the acid salts from the overhead oil layer, treating the mixed salt solutions with acid to regentially pure acetic, propionic, butyric, and highery acids.

- 3. The process of purifying a mixture of synthetically produced organic materials including hydrocarbons, oxygenated organic compounds, and water, which comprises subjecting the mixture of oily and aqueous products to a joint fractional distillation to recover an overhead product comprising light hydrocarbons, water, the major portion of the carbonyls and alcohols, and a minor proportion of the acids contained in the feed stock, and a bottoms product comprising heavier hydrocarbons, Water, the major portion of the acids, and a minor portion of the carbonyls and alcohols contained in the original charging stock, separating the overhead from the joint fractional distillation into an oily layer containing dissolved organicl compounds, and an aqueous layer containing alcohols and other Water soluble compounds, washing the oily layer whereby to strip therefrom additional water soluble compounds, combining the aqueous layer with the wash water from the oily layer, subjecting the combined aqueous solutions to a fractional distillation to recover therefrom as an overhead product a major portion of aldehydes'and ketones contained therein, and as a bottoms product an aqueous solution containing alcohols and a minor portion of the aldehydes and ketones contained therein, polymerizing the aldehydes and ketones contained in the bottoms product from the second fractional distillation, separating the resultant polymers, and subjecting the mixture of alcohols to a series of fractionations to separately recover ethanols, propanol, butanol, and higher alcohols.

4. The process as defined in claim 3 wherein the mixture of alcohols is further purified by azeotropic distillation with benzene prior to the series of fractionating operations.

IGNACE L. MALM.

REFERENCES CITED The followingreferences are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,684,640 Schmidt et al Sept. 18, 1928 1,704,751 Luther et al Mar. 12, 1929 1,870,816 Lewis Aug. 9, 1932 1,912,484 James June 6, 1933 2,076,607 Woodhouse Apr. 13, 1937 2,467,966 Clark Apr. 19, 1949 2,476,788 White July 19, 1949 2,482,284 Michel et al Sept. 20. 1949 OTHER REFERENCES Koch et al., Brenstoff Chemie, 16, 382 to 387 (1935).

Fischer, Conversion of Coal Into Oils, pages 242 to 245 (1925).

U. S. Naval Technical Mission in Europe, The Synthesis of Hydrocarbons and Chemicals from CO and H2, pages 84 to 92. 

1. THE PROCESS OF PURIFYING A MIXTURE OF SYNTHETICALLY PRODUCED ORGANIC MATERIALS INCLUDING HYDROCARBONS, OXYGENATED ORGANIC COMPOUNDS AND WATER, WHICH COMPRISES SUBJECTING THE MIXTURE OF OILY AND AQUEOUS PRODUCTS TO A JOINT FRACTIONAL DISTILLATION TO RECOVER AN OVERHEAD PRODUCT COMPRISING LIGHT HYDROCARBON, WATER, A LARGE PERCENTAGE OF THE CARBONYLS AND ALCOHOLS CONTAINED IN THE CHARGE STOCK AND A SMALL PERCENTAGE OF THE ACIDS CONTAINED THEREIN, AND A BOTTOMS PRODUCT COMPRISING HEAVIER HYDROCARBONS, WATER, A LARGE PERCENTAGE OF THE ACIDS CONTAINED IN THE CHARGING STOCK AND A SMALL PERCENTAGE OF THE CARBONYLS AND ALCOHOLS CONTAINED THEREIN, SEPARATING THE BOTTOMS PRODUCT INTO OILY AND AQUEOUS LAYERS, SUBJECTING THE AQUEOUS LAYER TO A SECOND FRACTIONAL DISTILLATION, WHEREBY TO SEPARATE THEREFROM AN OVERHEAD PRODUCT CONTAINING CARBONYLS AND 